DE2251349B2 - PROCESS FOR THE PRODUCTION OF MALEIC ACID ANHYDRIDE BY OXYDATION OF AN UNSATURATED HYDROCARBON - Google Patents

Description

Chromium to phosphorus is less than 1.0, a bismuth oxide, bismuth chloride, bismuth sulfate, etc. in

Bismuth compound or a titanium compound. If you have any questions

This process variant is in particular the precedent. Titanium compound can be titanium dioxide, titanium

partly achieved that no reduction in the catalytic nitrate, titanium sulfate, titanium trichloride, titanium tetrachloride

Use activity of the catalyst during reaction 5, etc.

entry. ... Are the metal compounds mentioned above

Furthermore, it is preferably used in the fertilizer for implementation as chlorides or sulfates, then

the reactor used during the process, chlorine or sulfate residues remain in the catalyst,

Reaction introduced a phosphorus compound. In which, however, no effect on the catalytic ac-

this procedural variant will also exert a high io tivity.

Yield without a decrease in the catalytic activity The introduction of the phosphorus compound in the for

of the catalyst achieved during the reaction. Implementation of the process used reactor

The inventively used, from oxides des can according to one of the methods described below

Tungsten and phosphorus existing catalyst methods can be carried out:

1) represents a mixture containing an oxide of Wolf 15

rams and contains an oxide of phosphorus, 2) a 1. A phosphorus compound becomes continuous

Complex or a compound of tungsten, phos or at intervals of the feed gas mixture

phosphorus and oxygen or 3) a mixture thereof. added,

This is the atomic ratio of tungsten to 2. A phosphorus compound is in the reactor

Phosphorus below 30 and preferably fluctuates 20 with or without an inert gas, such as water

between 1 and 18. steam, introduced,

In order to produce the catalyst used according to the invention 3. a phosphorus compound that is in a solution, 1) a tungsten compound that is dissolved in a medium, such as water, is added to a preferably composed of WO ₃ , H ₂ WO ₄ , H ₄ WO ₅ , (NH ₄ J ₂ WO ₄ , catalyst sprayed on, which consists of oxides of W ₄ O _n , W ₁₀ O ₂₉ , WCl ₆ , WBr ₆ , WCl ₅ , WBr ₅ , meta-25 tungsten and phosphorus, namely tungstic acid, ammonium metatungstate, ammo - rend or after the reaction, nium paratungstate, an alkali tungstate, a

Alkaline earth tungstate, etc. is selected and 2) a Phosphine can be used as a phosphorus compound,

Phosphorus compound, which is preferably composed of phosphorus-phosphorus oxide (preferably phosphorus pentoxide),

pentoxide, hypophosphorous acid, phosphorous 30 phosphorous acid, phosphorous acid, diphosphorous acid

Acid, diphosphorous acid, hypophosphorous acid, acid, hypophosphorous acid, orthophosphoric acid, me-

Orthophosphoric acid, metaphosphoric acid, ultraphosphoric acid, salts of phosphorous acid or

phosphoric acid, etc. is selected is used. Furthermore, phosphoric acid, which under the action of heat

a compound can be used that can decompose tungsten, such as ammonium

and contains phosphorus, such as phosphorus dihydrogen phosphate, triethylammonium phosphate

tungstic acid or a salt thereof. or an organophosphorus compound, which is preferred

As alkali compounds, oxides, hydroxides, from compounds of the formulas chlorides, carbonates, sulfates, nitrates, phosphates,
Acetates, etc. of alkali metals can be used.

Is the atomic ratio of the alkali metal to Phos 40

phor above 4.0, then the initial activity increases O O

of the catalytic converter. || Il

As alkaline earth metal compounds, oxides, R_p_x R_p_x RO —P-OX

Hydroxides, chlorides, carbonates, sulfates, nitrates, | | |

Phosphates, acetates, etc. from alkaline earth metals degrade 45 χ χ ΟΧ be turned.

Copper compounds can be copper (II) chloride, copper (I) chloride, copper (II) sulfate, copper

fer (I) sulfate, copper (II) nitrate, copper (I) nitrate, etc. is selected in which R is a phenyl or alkyl radical

use. If the atomic ratio to phosphorus is 50, and X is hydrogen or R, where ge

the catalyst above 2.0, then the Selek takes suitable compounds for example diethylphosphine,

activity with respect to maleic anhydride. Triethylphosphine, tribiitylphosphine oxide, triethylphosphine

As zinc compounds, zinc oxide, zinc phosphate and triphenyl phosphate can be used, chloride, zinc sulfate, zinc nitrate, etc. can be used. The following describes a typical method for the atomic ratio of zinc to phosphorus above 55 position of the catalyst mentioned. To -1.0, then the conversion decreases at the unsaturated next becomes a tungsten compound in an air hydrocarbon. current at a temperature of 400 to 1000 ⁰ C

As a molybdenum compound, molybdenum can be used for a period of 1 to 20 hours.

sesquioxide, molybdenum trioxide, ammonium molybdate extraction of a tungsten oxide calcined. Then it will be

etc. use. If the atomic ratio of molybdenum is 60, the tungsten oxide is mixed with phosphoric acid

to phosphorus above 1.0, then the selectivity decreases with a corresponding amount of water is diluted,

with respect to maleic anhydride. and possibly with a third connection.

Chromium oxide can be used as a chromium compound, then the mixture is used to obtain a

Chromium chloride, chromium phosphate, chromium sulfate, chromium paste-like mixture heated. By deforming

use acid, etc. Is the atomic ratio of 65 of the paste-like mixture to the desired size

Chromium to phosphorus above 1.0, then take the and by drying you can produce a catalyst.

Selectivity with respect to maleic anhydride. place. By calcining the thus obtained

As a bismuth compound come bismuth nitrate, the catalyst at a temperature of 300 to

C "» r Ut ρς möelich as a diluent for the

80O ⁰ C and preferably from 500 to 700 ⁰ C can also be «? ™ ^Ο ? ^ 1 of _a reaction outlet gas that

made even more stable and more active catalysts oxygen _use "" ^ ^.

will. v ^ r, ₇ "of the unsaturated carbon ntrate water

The oxides of phosphorus and tungsten and, if the K concentrates de uj ^B _{reaction mixture}

required, a third connection can be made on a 5 stoff> n em «^ P 8 ^ _ßreiches ^ J

Be deposited carrier. Grazing in this case varies J ™ g ™ ° _u ^e _ättigteil hydrocarbon

these materials by the following method up to the ^{e 'n} S ^"et f ^ J f ⁿ _for dilution used

After a shaped carrier my water and water, depending on the _{molar ratio} , of a _{certain amount} .

membered solution has been immersed, t _he a tungsten inert gas, bs is ud ^ oxygen to below

compound contains, or after a powdered i. of saturated ^cabbage ™ ^S _a ^e _{bef about} ι _{: 2} for serving

Carrier and tungsten oxide have been mixed, about 1. IU o> «r« ui, "- _n7USt eiien

whereupon the mixture in the desired size over- preventing an explosion «n ^? ^ has been carried out, the molded material is at a Um ^ »^ esgeinaß Matansau ^ nhydnd he

calcined elevated temperature, which provides a phosphorus, becomes a ^Κ8 ^ ^ο ^ _β Χί ^ ° 5 / ^

connection canceled. If necessary, there is also a 15 phor and tungsten as well as required ta a »

Immersion in an aqueous solution containing a third third component in ^ men reactor em ^

Contains component, at the same time or filled. Then. ^ ^Rf "™ ®f ° ™ * L" _n d absorbent material

separates. The oxygen deposited on a carrier after an unsaturated hydrocarbon

The catalyst obtained with this method can be used for oxygen or oxygen removal

can be used to carry out a reaction. He can put 20 reactor, fcs lsi

space velocity of 8j can of course also be used after calcination

the. Conventional carriers are used as carriers, a mixture between 500 and 15 "per weight

such as silica gel, aluminum oxide, diato- preferably between η 1500 andWW pn »

sea earth, alum, carbon dioxide, calcium sulphate, etc.

Of the unsaturated hydrocarbons with, 5, namely the highest temperature .η the catalyst

at least 4 carbon atoms, the layer according to the invention, between 2501 and 650 C una

can be used as feed material, between 350 and 500 C. _Vata , _{watnr in}

be for example butene-1, butene-2, butadiene, invention "according to ^" ^^. ^ fS ^ ° \ ^ _{5 8} ·.

Cyclopentadiene, pentene-1, a C ₄ fraction produced by a fixed bed, a fluidized bed or an I

Naphtha cracking is obtained, etc. mentioned. There is 30 moving bed to be used. It is to-

possible, also several unsaturated hydrocarbons, the catalyst in the form of a bed or

fabrics to use. To use for the manufacture of maleic acid a moving bed as the

Anhydride is used as an oxidizing agent, oxygen or a reaction to produce maleic anhydride

a gaseous mixture that contains oxygen as is exothermic. c _rfi "j

e.g. air, in addition to the above-mentioned 35 The following examples illustrate the invention,

unsaturated hydrocarbons are used. It is without limiting them. Here are the sales that

possible as oxidizing agent oxygen, mixed selectivity with respect to maleic anhydride as well

with an inert gas such as nitrogen, the yield is defined by the following equations.

Carbon dioxide, water vapor, etc. to use. ned:

Mo l of unsaturated hydrocarbon converted. Mol of unsaturated hydrocarbon used

Moles of maleic anhydride formed _inn

Selectivity =: r — r, - ~ Z * ^1ϋυ ·

Moles of unsaturated hydrocarbon reacted

Yield = conversion · selectivity.

55 tungsten 1: 6.3. The catalyst is then in one

. -I ₁ stream of air ^{calcined at 500 0} C for 2 hours.

Example 1 _The f _au <jj _ese ^ _e j _se catalyst is in

Filled into a reactor that has an inner diameter

50 g of tungstic acid are in a stream of air at 15 mm and has a length of 60 cm. Of a Temperalcr of 700 ⁰ C during a 60 temperature reactor is provided with a heater. Calcined at 700.degree. C. for a period of 4 hours while maintaining the temperatures given in Table I. 45 g of the tungsten oxide obtained, which is the highest in the catalyst layer with 3.55 g of phosphoric acid with a purity of, is air, 1 percent by volume of one of Ta-85% and water to produce a paste-like belle I specified unsaturated hydrocarbons mixture mixed. The mixture is molded, 65 or a mixture of these hydrocarbons, before the molded mass is dried. In the holding, the catalyst obtained by the above method was introduced into the reactor at a space velocity of 3000 per hour. The resultant substitute is the atomic ratio of phosphorus to results from Table I.

Table I. Unsaturated
Hydrocarbon temperature
( ⁰ C) yield
to Malein
acid
anhydride yield
to ge
more saturated
acid Sales
unsaturated
Coals
hydrogen attempt
No. Butene-1 460 67 2 96 1 cis-butene-2 460 66 3 98 2 trans-butene-2 460 68 2 95 3 Butadiene 460 74 1 100 4th Cyclopentadiene 480 54 2.2 95 5 Pentene-1 500 41 7.2 90 6th Dicyclopentadiene 480 49 3.1 90 7th Mixture that is 25 weight
parts butane, 48 weight
share η-butene and 29 Ge
contains important parts of isobutene 460 35 5 85 8th

Example 2

45 g of tungsten oxide, prepared by the same method as described in Example 1, are mixed with 7.0 g of phosphoric acid with a purity of 85% and water to produce a paste-like mixture, whereupon the mixture according to that described in Example 1 Way of working is processed. In the catalyst obtained, the atomic ratio of phosphorus to tungsten is 1: 3.2. The catalyst is then calcined in a stream of air at 500 ^° C. for 2 hours.

The catalyst obtained in this way is introduced into the same reactor that was used to carry out Example 1. While maintaining a temperature of 490 ⁰ C in the catalyst layer is air that contains 1 percent by volume of butene-1 introduced into the reactor at a space velocity of 3000 per hour. The yields of maleic anhydride and saturated acid are 60 and 1%, respectively, while the conversion of 1-butene is found to be 98%.

The deterioration in the yield of maleic anhydride during the reaction is shown in the table II emerged.

Table II

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

98 spi el 3 67 94 45 94 28 at

55 g of ammonium paratungstate are calcined in a stream of air at 700 ^° C. for 5 hours. 45 g of the tungsten oxide obtained are mixed with 3.55 g of phosphoric acid with a purity of 85% and with water to produce a paste-like mixture. The mixture is processed according to the procedure described in case 1. A catalyst is obtained with an atomic ratio of phosphorus to tungsten of 1: 6.3. The catalyst is then calcined in a stream of air at a temperature of 500 ^° C. for 2 hours.

Using this catalyst, the same reaction as in Example 1 is repeated. the Yields of maleic anhydride and saturates

14th
19th

0
1
1

1
1
4th

Acid amount to 54 or 2%, of the butene-1 conversion is determined to 97%

Example 4

45 g of tungsten oxide, which according to the be in Example 1 described method has been established with 2.0 g ammonium dihydrogen phosphate and water to create a paste-like mixture ver mixes. The mixture is subjected to the procedure described in Example 1, whereby eini Catalyst with an atomic ratio of phospho to tungsten of 1: 6.3 is obtained

Using this catalyst, the same reaction as in Example 1 is repeated Yields of maleic anhydride and saturated acids are 62 and 3%, respectively, and the butene-1 conversion is determined to 93%

609524 / 5C

Example 5

30 g of tungsten oxide are mixed with 15 g of a finely powdered silica gel which has been calcined at 800 ° C. for 2 hours, and then with 2.4 g of phosphoric acid with a purity of 85% and with water to produce a paste-like mixture. After drying at 100 ° C., the mixture is molded. Then, the molded material is calcined for 2 hours in an air stream at ⁰ C SOO.

The catalyst obtained in this way (P: W = 1: 6.3) is used in the for carrying out Example 1 used reactor filled. The temperature of the catalyst layer is regulated to 450 ° C. Air, which contains 1 percent by volume of butene-1 is fed into the reactor at a space velocity of 2,400 initiated per hour. The yields of maleic anhydride and saturated acids are 49 and 5%, while the 1-butene conversion is determined to be 96%.

Example 6

Phosphorotungstate (P ₂ O ₆ · 24 WO ₃ · nH ₂ 0) is calcined at a temperature of 700 ° C. for 4 hours and then crushed. Using the crushed material as a catalyst (P: W = 1:12), the same reaction as in Example 1 is repeated. The yields of maleic anhydride and saturated acids are 45 and 4%, respectively, while the conversion of 1-butene is found to be 97%.

Comparative example 1

Only powdered tungsten oxide is used as the catalyst for carrying out those described in Example 1 Reaction used. The maleic anhydride yield is 4%.

Example 7

50 g of tungstic acid are calcined in a stream of air at 800 ° C. for 3 hours. 45 g of the tungsten oxide obtained are mixed with an aqueous mixture containing 3.55 g of phosphoric acid with a purity

of 85% and contains 0.13 g of lithium chloride. A paste-like mixture is obtained. The paste-like Mixture is molded and then dried. The catalyst obtained in this way has a Atomic ratio of phosphorus to tungsten to lithium

ao thium of 1: 6.3: 0.1. The catalyst is then in calcined in a stream of air at 500 ° C. for 3 hours.

The catalyst obtained in this way is used in the example 1 carried out Reactor filled. The temperature in the catalytic

The sensor layer is regulated to 460 ° C. Air containing 1 percent by volume of butene-1 is fed into the reactor initiated at a space velocity of 3000 per hour. The results obtained are in Table III summarized.

Table III

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 98 49 32 15th 0 2 15th 98 52 31 12th 1 2 60 98 48 32 15th 0 3

Example 8

45 g of tungsten oxide, which has been obtained according to the procedure described in Example 7, are mixed with an aqueous mixture containing 3.55 g of phosphoric acid with a purity of 85% and 0.33 g Contains sodium chloride. A paste-like mixture is obtained. The paste-like mixture will deformed and then dried. The catalyst thus obtained has a ratio of phosphorus zn tungsten to sodium of 1: 6.3: 0.1. Of the The catalyst is then calcined in a stream of air at 500 ° C. for 3 hours. Using the on this The catalyst obtained in the manner described in Example 1 is carried out. The results are summarized in Table IV.

Table IV

Time after the Start of the reaction elapses

(Hours.)

Sales Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 94 58 26th 9 0 1 15th 90 55 24 9 0 2 60 91 599 21 8th 0 1

Example 9

The procedures described in Example 8 are repeated with the exception that butadiene is used as an unsaturated hydrocarbon in place of butene-1. The yields of maleic anhydride after 3, 15 and 50 hours from the start of the reaction, they are 65, 63 and 61%, respectively.

Example 10

45 g of tungsten oxide, which has been prepared according to the procedure described in Example 7, are

mixed with an aqueous mixture containing 3.55g phosphoric acid with a purity of 85% and contains 0.2 g of potassium carbonate. A paste-like mixture is obtained. The paste-like Mixture is treated according to the procedure described in Example 7 to produce a catalyst. The catalyst has an atomic ratio of phosphorus to tungsten to potassium of 1: 6.3: 0.1. Using this catalyst, the procedure described in Example 7 is repeated. the Results are shown in Table V.

Table V

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 96 65 21 9 0 1 15th 95 62 20th 11th 0 2 60 95 63 20th 11th 0 1

Example 11

Using the catalyst prepared according to Example 8, with the exception that the amount of sodium chloride used is changed, the same reaction as in the example 8 repeated. The results are shown in Table VI.

Mixture is used, which consists of 25 percent by weight butanes, 48 percent by weight η-butene and 27 Ge weight percent isobutene (instead of butene-1). The yields of maleic anhydride nacr 3, 15 and 50 hours from the start of the reaction are 33, 35 and 33%, respectively.

Example 13 Table VI

Experiment no. P: W: Well

Conversion of the yield of butene-1 maleic acid

anhydride

1 1: 6.3: 0.05 98 54 2 1: 6.3: 0.10 98 56 3 1: 6.3: 0.25 85 48 4th 1: 6.3: 0.50 12th 4th 5 1: 6.3: 1.00 8th 2

Example 12

The same procedure is followed as in Example 8, with the exception that a gaseous 50 g of tungstic acid are ^{calcined in a stream of air at 800 °} C. for 3 hours. 45 g of the resulting tungsten oxide are mixed with an aqueous mixture containing 7.0 g of phosphoric acid with a purity of 85% and 0.58 g of anhydrous magnesium chloride. This gives a paste-like mixture. The paste-like mixture is then shaped and dried. The atomic ratio:

Phosphorus to tungsten to magnesium in the catalyst obtained is 1: 3.2: 0.1. The Kataly sator is calcined for 2 Stundei in an air stream at 500 ⁰ C.

Using the above-described catalyst, the same reaction as in Bei Game 1 performed. The results are shown in Table VII.

Table VII

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 98 51 27 17th 11th 2 15th 98 52 28 15th 1 2 60 97 49 30th 14th 1 3

Example 14

45 g of tungsten oxide, which has been prepared according to the method described in Example 13, are mixed with an aqueous mixture containing 7.0 g of phosphoric acid with a purity of 85% and 1.5 g Contains barium chloride dihydrate. A paste-like mixture is obtained. The paste-like

Mixture is shaped and then dried. The atomic ratio of phosphorus to tungsten to barium in the catalyst obtained is 1: 3.2: 0.1. The catalyst is then calcined in a stream of air at 500 ^° C. for 3 hours.

Using this catalyst, the same reaction as in Example 13 is repeated. the Results are shown in Table VIII.

Table VIII

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 94 54 28 10 0 2 15th 94 48 24 8th 1 1 60 91 48 26th 9 0 2 Example 15 borrowed mixture deformed and < lan
η r -

45 g of tungsten oxide, which has been prepared according to the method described in Example 13, are mixed with an aqueous mixture which contains 7.0 g of phosphoric acid with a purity of 85% and 14.8 g of barium chloride dihydrate. A paste-like mixture is obtained. The atomic ratio of phosphorus to tungsten to barium in the catalyst obtained is 1: 3.2: 1. The catalyst is then calcined in a stream of air at 500 ^° C. for 3 hours.

Using this catalyst, the same reaction as in Example 13 is carried out. the Results are shown in Table IX.

Table IX

Time after the Start of the reaction elapses

(Hours.)

Sales Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

97 isp iel 16 52 98 56 94 55 Be

12th
9
9

0
1
0

5 3 2

given quantities mixed According to the example 1: A mixture of 45 g of tungsten oxide and 7.0 g of 45 is prepared. This catalyst is used for implementation Phosphoric acid with a purity of 85% is used with the reaction according to Example 13. Which he Calcium sulfate dihydrate in the results in Table X can be seen from Table X.

Table X Amount of P: W: Approx Yield to Maleic anhydride (%) 57 Attempt no. Calcin
sulfate diby after 3 hours after 30 hours after 60 hours 59 drats 54 (S) 54 1.0 1: 3.2: 0.1 48 54 58 1 5.2 1: 3.2: 0.5 62 58 57 I. 10.4 1: 3.2: 1.0 57 60 53 3 20.8 1: 3.2: 2.0 59 59 4th 0.1 1: 3.2: 0.01 60 58 * ·) 42.0 1: 3.2: 4.0 57 57 83.0 1: 3.2: 8.0 54 53 7 ***)

·) Reaction ^{temperature (0} Q: 490; space velocity (hour- ¹ ) · 1500.

*) Reaction ^{temperature (0} Q: 510; space velocity (hour - ¹ ): 1500.

·· *) Reaction ^{temperature (0} Q: 510; space velocity (hour- ¹ ): 1500.

Example 17

A catalyst is made from 45 g of tungsten oxide, 7 g of phosphoric acid with a purity of 85% and 0.7 g anhydrous calcium chloride prepared by the method described in Example 13. The atomic ratio from phosphorus to tungsten to calcium in that

Table XI

Catalyst is 1: 3.2: 0.1. The catalyst will calcined with air at a temperature of 500 "C for 3 hours.

Using this catalyst, the reaction described in Example 13 is repeated with the Exception that butadiene is used instead of butene-1. The results are shown in Table XI emerged.

Time after the
Start of the reaction
elapses

(Hours.)

Sales
Butene-1

Yield (%)

Maleic anhydride

Carbon monoxide carbon dioxide acetic acid

Aldehyde compounds

3 99 66 16 11th 5 1 15th 99 65 17th 12th 4th 1 60 100 63 17th 14th 3 3 Example 18 Table XII

Using the catalyst of Example 17, the reaction of Example 13 is repeated, with the exception that a mixture is used which consists of 25 percent by weight butane, 48 percent by weight η-butene and 27 percent by weight isobutene (instead of butene-1). The yields of maleic anhydride after 3, 15 and 60 hours, calculated from the start of the reaction, are 31, 34 and 35, respectively

Time after the Sales Yield to Start of the reaction Butene-1 Maleic anhydride elapses (Hours.) <%> (7.)

Example 19

45 g tungsten oxide, 5 g phosphoric acid with a purity of 85%, 1.0 g copper (I) chloride and a corresponding amount of water are mixed to produce a paste-like mixture. The paste-like mixture is molded and calcined, and then dried for 2 hours in an air stream at 50O ⁰ C.

Using this catalyst (P: W: Cu = 1: 4.5: 0.23) the reaction according to Example 1 is repeated. The results are summarized in Table XII.

3 89 20th 58 15th 98 59 60 98 60 example

The catalysts (I) to (V) are prepared by the method described in Example 19 from 45 g of tungsten oxide, 7 g of phosphoric acid with a purity of 85% and yet another component, its type and Amount given in Table XIII.

The reaction described in Example 19 is repeated using catalysts (I) to (V). The results are summarized in Table XIV.

catalyst

Tungsten Oxide Phosphoric Acid with Other Component
a purity
from 85%

(g) (g) (g)

I. P: W: Zn = 1: 3.2: 0.1 45 7th II P: W: Mon = 1: 3.2: 0.1 45 7th III P: W: Cr = 1: 3.2: 0.1 45 7th IV P: W: Bi = 1: 3.2: 0.1 45 7th V P: W: Ti = 1: 3.2: 0.1 45 7th VI P: W: Ti = 1: 3.2: 0.5 45 7th VII P: W: Ti = 1: 6.4: 10 45 3.5 VIII P: W: Ti = 1: 6.4: 20 45 3.5 IX P: W: Bi = 1: 3.2: 0.5 45 7th X P: W: Bi = 1:10:10 45 2.2

Zinc chloride, 0.8
Ammonium molybdate 1.1
Chromium nitrate 2.4
Bismuth nitrate 2.9
Titanium tetrachloride 1,2
TiCl ₃ (20%, remainder water) 23

TiO ₂ 24

TiCl ₃ (20%, remainder water) 0.23

TiO ₂ 48

TiCl ₃ (20%, remainder water) 0.23

Bi (NOa) ₃ · _{5H 2} O 15
Bi (NO ₃ ), · 5 H _S O 94

Table XIV A catalyst Sales Butene-l (%) after 60 hours Maleic anhydride yield {%) after 15 hours after 60 hours catalyst after 3 sui. after 15 Sta. 95 after 3 hours 57 54 95 95 99 59 57 57 I. 99 99 100 58 50 51 II 100 100 90 52 43 50 III 91 90 100 54 60 64 IV 100 100 99 64 62 80 V 99 99 80 63 58 59 VI 82 80 74 58 57 56 VII 79 75 80 57 50 54 VIII 80 81 72 48 40 44 IX 75 72 and 42 Example 23 X the off 45 grams of tungsten oxide

3.55 g of phosphoric acid with a purity of 85% has been produced (P: W = 1: 6.3), is in a Given reactor with an internal diameter of 15 mm and a length of 600 mm. The reactor is with a heating device and a spray device for spraying phosphoric acid. In the Air containing 1 percent by volume of butene-1 is introduced into the reactor at a space velocity from 3000 per hour. An aqueous solution containing 10 percent by weight phosphoric acid is used atomized by means of the spray device in an amount of 2 g per day. The yields of maleic anhydride after 3, 30 and 300 hours are 62, 62 and 60%, respectively.

Example 22

The procedure described in Example 21 is repeated, with the exception that an aqueous one Solution containing 10 percent by weight of triammonium phosphate is used in place of the aqueous solution containing 10 percent by weight phosphoric acid, furthermore using a catalyst composed of 45 g tungsten oxide, 7 g phosphoric acid with a purity of 8'5% and 0.8 g zinc chloride (P: W: Zn = 1: 3.2: 0.1).

The yields of maleic anhydride after 3, 30 and 300 hours, calculated from the start of the reaction, are 59, 63 and 63%, respectively.

Catalyst combinations according to the invention with the P: W atomic ratios given in the table below are prepared according to the method described in Example 1, with the exception that Ammonium diphosphate is used instead of phosphoric acid.

The reaction described in Example 1 is carried out using these catalysts, butene being used as the unsaturated hydrocarbon. The results obtained are summarized in Table XV:
35

Tabel XV 40 1 relationship Reaction Yield to Experiment no. P: W atom 45 2 temperature Maleic acid 3 anhydride 4th 1:50 ( ⁰ C) CA) 5 1: 16.7 420 24 50 6 1: 6.3 430 59 1: 3.2 460 68 1: 1 490 67.5 1: 0.32 505 61 520 49

Claims (3)

Tungsten is described in JA-PS 9688/62. In the patent claims: Using this catalyst, however, the yield of maleic anhydride is still unsatisfactory. 1. Processes for the preparation of maleic acid-vanadium oxide containing catalysts are also used anhydride by oxidation of an unsaturated 5 in the DT-AS 12 92 649 and 13 02 116, in the DT-OS Hydrocarbons of at least 4 carbon 19 00 111 and 14 68 814 and in US Pat. No. 3,366,648 atoms or a mixture of such and 22 06 377 described. Hydrocarbons with oxygen in the gas using the known method phase at elevated temperature over a catalyst containing Wolf vanadium oxide adheres Ram and phosphorus-containing oxide catalyst, but the disadvantage that the yields achieved characterized in that maleic anhydride, partly as a result of the formation uses a catalyst made up of oxides of by-products, which are not particularly high. There is tungsten and phosphorus, whereby the invention has therefore set itself the task of Atomic ratio of tungsten to phosphorus under- create a process when it is carried out half past 30 is. 15 achieved a high yield of maleic anhydride 2. The method according to claim 1, characterized in that the formation of by-products, such as draws that the catalyst additionally suppressed an AI, for example acetic acid and aldehydes potassium metal compound, where the atomic ratio becomes. from alkali metal to phosphorus is less than 0.4 This task is performed in a process that registers, an alkaline earth metal compound, the type described above being solved by one Atomic ratio of alkaline earth metal to phosphorus uses a catalyst composed of oxides of the is between about 0.001 and 100, a tungsten and phosphorus, the Copper compound, with the atomic ratio of atomic ratio of tungsten to phosphorus below Copper to phosphorus is less than 2.0, a 30 is. Zinc compound, the atomic ratio being 25 When performing this process, it is possible-zinc to phosphorus is less than 1.0, an Hch, to a high yield of maleic anhydride Molybdenum compound, achieving the atomic ratio and the formation of by-products prevent from molybdenum to phosphorus less than 1.0. It is surprising that, if one carries, a chromium compound, the atomic vanadium compound, which is generally referred to as a catalysis ratio from chromium to phosphorus is less than 1.0 30 sator for the production of maleic anhydride, a bismuth compound or a titanium compound is used, one used according to the invention connection contains. Catalyst is added, a deteriorated cat- 3. The method according to claim 1 or 2, characterized lytic activity is the result, wherein the yield characterized in that one decreases in maleic anhydride in the implementation. of the process used reactor during the 35 phosphorus compounds have on their own Reaction introduces a phosphorus compound. no catalytic activity related to manufacture of maleic anhydride by oxidation of an unsaturated hydrocarbon having at least 4 carbon atoms. The same applies to Wolframverbin-40 fertilize, which is of very low selectivity with respect to the generation of maleic anhydride, if ——— they are used alone. It was therefore over surprising that a combination of the oxides of phosphorus and tungsten to catalyze the oxidation 45 of an unsaturated hydrocarbon having at least 4 carbon atoms is so effective that yields can be achieved, which is significantly above the yields The invention relates to a method of manufacture, which are achieved in methods of their »On maleic anhydride by oxidation of an un- carrying catalysts that are used E! Contain saturated hydrocarbons with at least 4 carbon 50 vanadium oxide,
atomic atoms or a mixture of such The atomic ratio of tungsten to phosphorus, Hydrocarbons with oxygen in the gas phase, which must be below 30, play a role in the flow elevated temperature over a tungsten and implementation of the method according to the invention a Oxide catalyst containing phosphorus. critical role, as in particular from the one below Maleic anhydride is known to be obtained from Example 23 below.
According to a preferred embodiment, contains oxidation of an unsaturated hydrocarbon more than 4 carbon atoms in the presence of one of the catalysts additionally an alkali metal compound catalyst, The vanadium oxide contains, made manure, where the atomic ratio of alkali metal to can be. However, vanadium oxide alone as phosphorus is less than 0.4, an alkaline earth metal catalyst used, then the yield of 60 compound, where the atomic ratio of alkaline earth maleic anhydride quite low. In order to convert the metal to phosphorus between approximately 0.001 and 100 Interpretation of maleic anhydride in the event that a copper compound is available, whereby the atomic ratio that a catalyst is used which is from copper to phosphorus less than 2.0, Containing vanadium oxide is generally a Co- a zinc compound, the atomic ratio being of catalyst, such as a molybdenum oxide, a 65 zinc to phosphorus is less than 1.0, a Mo-tungsten oxide or a phosphorus oxide, the catalysis compound, the atomic ratio of added sator. For example, a molybdenum to phosphorus catalyst will be less than 0.1 from vanadium pentoxide and oxides of phosphorus and chromium compound, the atomic ratio of